Synthesis of Highly Functionalized Triarylbismuthines by Functional Group Manipulation and Use in Palladium- and Copper-Catalyzed Arylation Reactions.

Organobismuthines are an attractive class of organometallic reagents that can be accessed from inexpensive and nontoxic bismuth salts. Triarylbismuthines are particularly interesting due to their air and moisture stability and high functional group tolerance. We report herein a detailed study on the preparation of highly functionalized triarylbismuth reagents by triple functional group manipulation and their use in palladium- and copper-catalyzed C-, N-, and O-arylation reactions.

Copper-catalyzed O-arylation of N-protected 1,2-aminoalcohols using functionalized trivalent organobismuth reagents.

The O-arylation of 1,2-aminoalcohols using functionalized triarylbismuth reagents is reported. The reaction can be performed using substoichiometric amounts of copper acetate and operates under mild conditions. Good functional group tolerance is observed, giving access to a range of ß-aryloxyamines. The effect provided by the amino group in the arylation reaction is investigated.

Synthesis of highly functionalized diaryl ethers by copper-mediated O-arylation of phenols using trivalent arylbismuth reagents.

Highly functionalized diaryl ethers were prepared by copper(II) acetate mediated O-arylation reaction of phenols using trivalent organobismuthanes. The reaction is performed under simple conditions and tolerates a wide diversity of functional groups on the phenol and on the organobismuth reagent. Substoichiometric amounts of catalyst can be used by performing the reaction under an oxygen atmosphere. The N-arylation of pyridones is also reported.